WO2016092010A1 - Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde - Google Patents

Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde Download PDF

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Publication number
WO2016092010A1
WO2016092010A1 PCT/EP2015/079234 EP2015079234W WO2016092010A1 WO 2016092010 A1 WO2016092010 A1 WO 2016092010A1 EP 2015079234 W EP2015079234 W EP 2015079234W WO 2016092010 A1 WO2016092010 A1 WO 2016092010A1
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WIPO (PCT)
Prior art keywords
imidazoline
use according
amido
tofa
tallow
Prior art date
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PCT/EP2015/079234
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English (en)
Inventor
Nihal Obeyesekere
Thenuka Ariyaratna
Jonathan Wylde
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Clariant International Ltd
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Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to EP15807923.6A priority Critical patent/EP3230398B1/fr
Priority to CA2962751A priority patent/CA2962751C/fr
Priority to EA201791291A priority patent/EA034845B1/ru
Priority to US15/534,307 priority patent/US10611951B2/en
Priority to DK15807923T priority patent/DK3230398T3/da
Publication of WO2016092010A1 publication Critical patent/WO2016092010A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • the invention described concerns corrosion inhibitors, especially corrosion inhibitors when applied to saturated and concentrated salt solutions.
  • the application of these corrosion inhibitors is particularly suited to oilfield exploration, drilling, production and process systems where brines such as sodium chloride, calcium chloride, calcium bromide, zinc bromide, calcium nitrate and other salt brines and mixtures thereof (hereinafter also referred to as "heavy brines") are basic components for operation processes.
  • brines such as sodium chloride, calcium chloride, calcium bromide, zinc bromide, calcium nitrate and other salt brines and mixtures thereof (hereinafter also referred to as "heavy brines") are basic components for operation processes.
  • the application of these inhibitors protects the metal surfaces that are exposed to the brines at ambient and elevated temperatures and where corrosion protection needs to be provided rapidly to reduce the corrosion rates to negligible levels.
  • Heavy brines are used during many different stages of the oil and gas exploration, drilling and production cycle, particularly as a component of drilling fluids, packer fluids, work-over fluids, kill fluids and completion fluids.
  • Packer fluids are used in the annulus of a well that surrounds the production tubing; work-over fluids are those used during remedial operations of a well; kill fluids are used to suspend a well either temporarily or permanently by hydrostatically over-balancing it with heavy brine; completion fluids are used after a well has been drilled but before the well has been brought online to production.
  • Heavy brines are used in drilling and well completion operations and can be is defined as a water containing a high concentration of dissolved inorganic salts. More specifically a heavy brine is defined as a water-based solution of inorganic salts used as a well-control fluid during the completion and work-over phases of well operations. Heavy brines are solids free, containing no particles that might plug or damage a producing formation. In addition, the salts in heavy brine can inhibit undesirable formation reactions such as clay swelling.
  • Brines are typically formulated and prepared for specific conditions, with a range of salts available to achieve densities ranging from 8.4 to over 22 lb/gal (ppg) [1 .0 to 2.65 g/cm 3 ] but more commonly from 10 to 18 lb/gal (ppg) [1 .2 to 2.2 g/cm 3 ] and even more commonly between 1 1 .5 to over 17 lb/gal (ppg) [1 .4 to 2.0 g/cm 3 ].
  • a brine is considered to be a heavy brine in the sense of this invention if its density is 1 .15 g/cm 3 or above, more preferably 1 .2 g/cm 3 or above, still more preferably 1 .4 g/cm 3 or above.
  • the preferred upper limit of density is 2.65 g/cm 3 .
  • Preferred ranges of density are 1 .2 to 2.65 g/cm 3 , more preferably 1 .4 to 2.2 g/cm 3 , still more preferably 1 .5 to 2.0 g/cm 3 .
  • Common salts used in the preparation of simple brine or heavy brine systems may include, but are not limited to, single salts or mixtures of multiple salts comprising sodium chloride, calcium chloride, calcium nitrate and potassium chloride.
  • More complex brine or heavy brine systems may include, but are not limited to, single salts or mixtures of multiple salts comprising calcium bromide, zinc bromide or zinc iodine salts. These complex brines are generally corrosive and costly.
  • a particular challenge with heavy brines is their corrosivity. This is brought about by a few different features of the heavy brines. Firstly, the heavy brines tend to be saturated with respect to oxygen; secondly the heavy brines are strongly electrolytic and allow for efficient electron transfer and therefore corrosion; finally the heavy brines themselves can be of a very low pH.
  • the first set involves the use of metal salts. US-8007689 utilizes metalloids of antimony or germanium. It further discloses a more complex blend of morpholine derivatives, an unsaturated alcohol and an organic acid with at least two of these components together in any given blend. The mechanism is likely to be oxygen scavenging from the reducing agents and also passivation of the metal surface using the metalloids.
  • US-4849171 discloses the use of MgO used as an intensifier with super phosphate being contained in the overall blend. Again this is a passivating mechanism that offers the corrosion control.
  • US-4997583 teaches arsenic salts as the corrosion inhibitor, either alone or in combination with an admixture of urea (as a synergist).
  • Arsenic is AS2O3, AsBr3, or NaAs2O5 typically added at 200 ppm (arsenic).
  • US-2008/0274013 discloses the use of molybdenum oxide, and compounds based on antimony, copper and bismuth. These are used in combination with acetylenic amines or acetylenic alcohols.
  • EP-0153192 uses mono- and divalent salts of erythorbic acid and gluconate (sodium and iron salts). This can be made in a solid or liquid form. It is co-blended with alkali metals, specifically molybdate salts are added. The mechanism is unclear, but is postulated as scavenging combined with a chelation effect.
  • US-4536302 discusses the use of sulfur compounds where the oxidation state is either 0 or >0.
  • Thiocyanate or thio amide is used at concentrations as high as 1 g/L.
  • the reference discloses the addition of a reducing sugar (mono-saccharide, disaccharide or oligosaccharides) such as glucose, fructose, lactose, etc. These sugars are added at even higher rates of 2 to 10 g/L.
  • US-4728446 describes a corrosion inhibitor composition containing an alkali or alkaline-earth metal halide in water, zinc ions and thiocyanate ions.
  • US-4784778 and US-4784779 disclose the use of 2-mercaptoethanol, sodium, ammonia and/or calcium thiocyanate, with or without the addition of aldose based antioxidants such as arabinose, ascorbic acid, isoascorbic acid, gluconic acid etc.
  • aldose based antioxidants such as arabinose, ascorbic acid, isoascorbic acid, gluconic acid etc.
  • Ammonium thioglycolate is also mentioned as an additional component. It is noteworthy that very high concentration of inhibitor is required in the experimental data.
  • US-4980074 discloses the corrosion inhibitor as a blend of soluble aliphatic or aromatic aldehydes with or without olefinic unsaturation in combination with an alkali metal, thiocyanates or ammonium thiocyanates.
  • EP-0139260 discusses phosphorus containing compounds and the use of phosphonium salts such as triphenylphosphine. This is in combination with thiocyanate as well as a commercial product being added called "TRETOLITETM KI-86". "TRETOLITETM KI-86" is disclosed as a Mannich amine-based formulation.
  • WO-2009/076258 teaches a bis-quaternized compound for inhibiting corrosion and/or removing hydrocarbonaceaus deposits in oil and gas applications, the compound having a general formula: R 1
  • R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of: an unsubstituted branched, chain, or ring alkyl or alkenyl having from 1 to about 29 carbon atoms in its main chain; a partially or fully substituted branched, chain, or ring alkyl or alkenyl having from 1 to about 29 carbon atoms in its main chain, wherein said substitution includes being oxygenized, sulfurized, and/or phosphorylized; and combinations thereof;
  • L 1 and L 2 is each a moiety independently selected from the group consisting of: -H, -CO2H, -SO3H, -PO3H2, -CO2R 4 , -CONH2, -CONHR 4 , -CON(R 4 ) 2 , and combinations thereof; wherein each R 4 is independently selected from the group consisting of: branched or unbranched alkyl, aryk, alkylaryl, cycloalkyl, and heteroaromatic groups having from 1 to about 10 carbon atoms, and combinations thereof;
  • (c) x is from 1 to about 10;
  • compositions comprising at least one compound that is a ring-opened derivative of a C5-C21 alkylhydroxyethyl imidazoline and a
  • amphoacetates alkylamidoamineglycinates or
  • amphocarboxyglycinates Two other groups are di-acetates and amphosulfonates.
  • the ring-opened derivatives of C5-C21 alkylhydroxyethyl imidazolines are disclosed be especially effective when used in combination with alkyl quaternary amines (alkyl quats) and/or alkyl quaternary esteramines (ester quats).
  • alkyl quats alkyl quats
  • ester quats alkyl quaternary esteramines
  • the corrosion caused by heavy brines is fundamentally different to that which occurs during normal production operations when regular brines are used.
  • Regular brines are the subject matter of the WO-2009/076258 and WO-2012/063055 references. Corrosion in normal production operations (such as that described in WO-2009/076258 and WO-2012/063055) involves brines with a density
  • Brine A (WO-2012/063055) is fairly saline but is still much less that even the lightest brine (KCI) used in well service operations and general well work. Furthermore Brine A is a typical produced water composition and is composed of multiple salt compositions which is not the case for the artificially created heavy brines for completion and drilling operations.
  • compositions for inhibiting the corrosion of iron and ferrous metals in heavy brines comprising, as active constituent, at least one alkyl- poly(ethyleneamino)-imidazoline or 2-alkyl-poly-3-(ethyleneamino)-1 ,3-diazoline, corresponding to the general formula
  • R is a linear or branched, saturated or unsaturated hydrocarbon chain containing 10 to 22 carbon atoms, and in which n is a number from 0 to 3, and at least one mercapto acid corresponding to the general formula
  • n 0 to 3
  • R 1 is H or SH
  • R 2 and R 3 together or independently is C1-C4, CON(R 6 )(R 7 ) or COOR 8 ,
  • R 4 and R 5 together or independently is OH, NH2 or SH when R 1 ⁇ SH,
  • R 6 and R 7 together or independently is H or C1-C4,
  • R 8 is H or Ci-C 8 ,
  • the molar ratio between the mercapto acid component(s) and the imidazoline component(s) being from 1 .0 to 1 .5.
  • US-6149834 is not for oilfield use, rather is for inhibiting chloride salts used in de-icing application - relevant in a technical sense.
  • the corrosion inhibitor is composed of de-sugared sugar beet molasses where 5 to 25 wt% is applied versus the chloride salt, furthermore small amounts of associated zinc and phosphorus salts were reported as boosting performance.
  • US-4046197 names a commercial product (Corexit 7720) used in conjunction with a delivery system for a salt suspension.
  • WO-2000/039359 discloses the use of chelating agents such as
  • PBTC 2-phosphonobutane-1 ,2,4-tricarboxylic acid
  • HPA hydroxyphosphone-acetic acid
  • POCA phosphonocarboxylic acid
  • Azoles are also added such as mercapto benzotriazoles (MBT), benzotriazoles (BT), tolyltriazoles, etc.
  • Corrosion inhibitors for protection while using stimulation acids are also relevant because there are similarities in the arts when compared to heavy brine inhibitors.
  • US-2006/0264335 discloses the use of terpenes as intensifiers, for example carotene, limonene, camphor, menthol, etc.
  • US-651 1613 uses propargyl alcohol as the main inhibitor with iodine containing compounds as an intensifier. This is perhaps the most commonly used method in the art of protection against acidic corrosion inhibition.
  • US-5976416 discusses a more classic approach, for organic acid corrosion inhibition, where quaternary ammonium salts and activators are combined with thioglycolic acid and thiosulfates.
  • the intention of the current invention is to deliver new corrosion inhibitor formulations that lower the corrosion rates to negligible levels in heavy brine fluids.
  • a corrosion rate may be considered to be negligible if it is ⁇ 4 milli-inches per year, hereinafter mpy.
  • an object of the present invention to provide much higher performance than the existing art.
  • an object of the present invention to be applicable and compatible in all oil industry used heavy brine types including calcium nitrate which is often not specifically mentioned in the art.
  • an object of the present invention to provide a product that can function efficiently and to the desired level of corrosion control without the addition of an oxygen scavenging, or reducing agent.
  • an object of the current invention to provide corrosion protection particularly at high temperature, as well as low temperature performance, due to the trend to drill deeper, hotter, higher pressure wells. It is further, an object of the present invention to provide a corrosion inhibitor that is composed completely of organic based components with no salts or inorganic components, and especially no heavy metals, therefore providing an environmentally acceptable corrosion inhibitor package. It is further another object of the present invention to provide a corrosion inhibitor that does not induce, or contribute to in any way, additional risk of stress corrosion cracking. Yet another objective of the present invention is to prepare a corrosion inhibitor package composed of several ingredients and combination of ingredients to allow flexibility and therefore a more ubiquitous use around the world given the different legislations in place. Still another object of the present invention is to provide a formulation that kinetically reduces the corrosion rate much faster than any other products described in the art.
  • the present invention provides the use of a composition comprising
  • At least one sulfur synergist at least one sulfur synergist
  • the composition comprises additionally
  • the present invention provides a method for inhibiting corrosion caused by heavy brines, the method comprising adding the composition of the first aspect as corrosion inhibitor to heavy brine containing systems having a density of 1 .15 to 2.65 g/l.
  • this invention relates to the use of a phosphate ester to improve corrosion inhibition in a heavy brine, the heavy brine comprising at least one imidazoline and at least one sulfur synergist and having a density of 1 .15 to 2.65 g/l.
  • the composition will contain at least one component from each of groups 1 , 2, and 3.
  • a component from group 4 is present with the components from each of groups 1 , 2, and 3.
  • a component from group 5 is present with the components from each of groups 1 , 2, and 3.
  • both components from groups 4 and 5 are present with the components from each of groups 1 , 2, and 3.
  • Group 1
  • the compounds according to group 1 are preferably prepared by the condensation of an ethylenediamine compound (I) with an acid or ester compound (II) that results in the formation of an imidazoline (III) and an amidoamine (IV).
  • R is -H, -C 2 H NH 2 , -C 2 H OH, -(C2H NH) X -C 2 H NH2
  • x is a number from 0 to 200
  • R1 is a C3 to C29 aliphatic hydrocarbon group.
  • Formula II depicts an ester
  • R2 is H or a residue derived from Methanol, Ethanol, Isopropanol, Glycol or Glycerol by abstraction of one hydrogen atom from an OH group.
  • R1 is selected from straight alkyl, mono unsaturated alkenyl, di unsaturated alkenyl, tri unsaturated alkeny, oligo unsaturated alkyl, branched alkyl and cyclic alkyl. More preferred R1 has a chain length of 7 to 21 , particularly of 1 1 to 17 carbon atoms. Likewise more preferred is that R1 is selected from linear or branched alkyl, monounsaturated alkenyl or diunsaturated alkenyl.
  • R1 may represent a natural occurring hydrocarbon distribution or mixtures of the above mentioned hydrocarbon moieties.
  • R1 is the carbon chain of the acid or ester compound (II).
  • the acid or ester compound (II) is preferably selected from tall oil fatty acid and its derivatives (TOFA), coconut oil and its derivatives, tallow fatty acid and its derivatives (Tallow), naphthenic acids and its derivatives, soya fatty acid and its derivatives (Soya), oleic acid and its derivatives.
  • the ethylenediamine compound (I) is preferably selected from
  • TEPA tetraethylenepentamine
  • DETA diethylenetriamine
  • TETA triethylentetramine
  • AEEA aminoethylethanolamine
  • R results from the ethylenediamine compound substitution and, as described above, most commonly is either TEPA, TETA, DETA, AEEA and polyamine.
  • TOFA/polyamine amido imidazoline 2:1 TOFA/polyamine bisimidazoline, 3:1 TOFA/TEPA polyamine amido bisimidazoline, 1 :1 Soya/DETA imidazoline, 2:1 Soya/DETA amido-imidazoline, 1 :1 Soya /TETA imidazoline, 2:1 Soya/TETA amido-imidazoline, 2:1 Soya/TETA bismidazoline, 1 :1 Soya/TEPA imidazoline, 2:1 Soya/TEPA amido imidazoline, 2:1 Soya/TEPA bisimidazoline, 3:1 TOFA/TEPA amido bisimidazoline, 1 :1 Soya/AEEA imidazoline, 2:1 Soya/AEEA
  • amidoimidazoline 1 :1 Soya/polyamine imidazoline, 2:1 Soya/polyamine imidazoline, 2:1 Soya/polyamine amido imidazoline, 2:1 Soya/polyamine bisimidazoline, 1 :1 Tallow/DETA imidazoline, 2:1 Tallow/DETA amido-imidazoline, 1 :1 Tallow/TETA imidazoline, 2:1 Tallow/TETA amido-imidazoline, 2:1
  • Tallow/TETA bismidazoline 1 :1 Tallow/TEPA imidazoline, 2:1 Tallow/TEPA amido imidazoline, 2:1 Tallow/TEPA bisimidazoline, 3:1 Tallow/TEPA amido
  • Tallow/polyamine amido imidazoline 2:1 Tallow/polyamine bisimidazoline and 3:1 Tallow/TEPA poly amine amido bisimidazoline - there are also products that have different molar ratios of acid to amine and all molar ratios can be considered for the corrosion inhibiting formulations in the instant Application.
  • the molar ratios above refer to the molar amounts of the compounds according to formulae (I) and
  • the imidazoline is preferably selected from TOFA-DETA imidazoline, TOFA- polyamine imidazoline or TOFA-TEPA imidazoline.
  • One preferred embodiment of the invention is to use a 1 :1 Tallow/DETA
  • Another preferred embodiment is to use a 1 :1 Tallow/TEPA imidazoline as described in the Figure below:
  • Yet another preferred embodiment is to use a 1/1 Soya/AEEA imidazoline as described in the Figure below:
  • the sulfur synergists are generically any sulfur containing compound, either ionic or covalent by nature
  • R5 and/or R6 are H, Ci to Cio alkyl, C2 to C10 alkene or
  • the sulfur synergists are preferably selected from the group consisting of thioglycolic acid, sodium thiosulfate, ammonium thiosulfite, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, potassium thiosulfite, thiourea, sodium thiocyanate, ammonium thiocyanate, and calcium thiocyanate, sodium
  • thioglycolate ammonium thioglycolate
  • polythioureas and derviatives such as 1 ,2-diethylthiourea, propylthiourea, 1 ,1 -diphenylthiourea, thiocarbanilide,
  • One preferred sulfur synergist is thioglycolic acid whose structure is:
  • 2-mercaptoethanol is used, whose structure is:
  • ammonium thiosulfate is used, whose structure is:
  • phosphate esters or organophosphates are preferably of the generic formula:
  • Ra, Rb and Rc independently are selected from H or a hydrocarbon group, which may contain oxygen or nitrogen atoms, with a carbon atom number ranging from 1 to 49.
  • At least one of Ra, Rb and Rc are ethoxy groups.
  • said hydrocarbon group is composed of an alkyl or alkenyl residue.
  • the number of carbon atoms in Ra, Rb or Rc is from 4 to 30 carbon atoms, preferably 8 to 22, more preferably 12 to 18 carbon atoms.
  • Ra, Rb and Rc may be terminated by hydrogen.
  • the terminal hydrogen atom may be substituted by hydroxyl, benzyl or carboxylic acid groups.
  • the carbon chains themselves may be saturated or unsaturated depending on the source of the carbon chain species or degree of ethoxylation. In one embodiment, they contain intra-hydrocarbon chain groups such as carboxyl group (-COO-), oxygen (-O-), or a secondary amine group (-NH-). Intra-hydrocarbon means that such groups are not terminal groups.
  • 2-ethylhexylester is the phosphate ester species used, the structure of which has been displayed below:
  • Still another preferred embodiment of the invention uses lauryl polyoxethyl (4EO) phosphate ester sodium salts:
  • Yet another preferred embodiment of the invention uses stearyl polyoxethyl (4EO) phosphate ester sodium salts:
  • Yet another preferred embodiment of the invention uses tristyryl phenol ether phosphate, acid form:
  • the formulation bonding surfactants comprise the last group of components that bind the synergistic blend of other components together.
  • the definition of a bonding surfactant in this context is a component that enables the blend of all components to remain as a single phase with no separation or precipitation of solids.
  • the addition of this component is necessary typically because the components from Groups 1 , 2 and 3 display surfactant like properties and can be of a very varied Hydrophilic Lipophilic Balance (HLB). As a result of this it is very typical for these components to be otherwise incompatible with one another due to immiscibility.
  • HLB Hydrophilic Lipophilic Balance
  • the addition of a bonding surfactant (or mutual solvent) modifies the surface tension between the components to become more equal to one another and therefore enabling a single phase formulation.
  • R3 is H, Ci to Cie alkyl, Ci to Cs alkylamine
  • R3 is H, Ci to Cie alkyl, Ci to Cs alkylamine
  • the morpholine compounds may comprise alkyl morpholine and its derivatives, alkylaminomorpholine and its derivatives, alkyl morpholine oxides, alkylaminomorpholine oxide and its derivatives or any other morpholinyl structure.
  • N-methylmorpholine was used; in another preferred embodiment, N-ethylmorpholine was used; in yet another preferred embodiment, N-methylmorpholine oxide was used; in yet another preferred embodiment, Aminopropylmorpholine was used.
  • Nonyl phenol ethoxylates the nonyl phenol ethoxylates were used to assist the formulation of components described above to bond together.
  • the degree of ethoxylation can range from 4 moles of ethylene oxide (EO) to 100 moles of ethylene oxide.
  • the degree of ethoxylation is preferably from 6 to 60, more preferably from 9 to 40.
  • a nonyl phenol ethoxylate with 4 moles of EO was used; in another preferred embodiment a nonyl phenol ethoxylate with 6 moles of EO was used; in yet another preferred embodiment, a nonyl phenol ethoxylate with 9 moles of EO was used; in yet another preferred embodiment a nonyl phenol ethoxylate with 60 moles of EO was used.
  • R4 is an aliphatic Cs to Cie hydrocarbon residue
  • A is an ethylene group
  • x is a number from 2 to 100.
  • R4 is alkyl or alkenyl.
  • R4 may either be straight chain or branched.
  • R4 comprises from 12 to 16 carbon atoms.
  • x is a number from 7 to 40, more preferably from 10 to 20.
  • a linear C12/C14 alcohol with 7 moles of EO was used; in another preferred embodiment, a coconut (C12 to C16) fatty alkyl ethoxylate was used with 20 moles of EO; in yet another preferred embodiment, a C13 branched (isotridecyl) alcohol was used with 40 moles of EO was used; in yet another preferred embodiment, a C12/C15 oxo alcohol ethoxylate with 10 moles of EO was used.
  • R4 is an aliphatic C6 to Cie hydrocarbon residue
  • A is an ethylene group
  • x is a number from 2 to 100.
  • R4 is an aliphatic C6 to C18 hydrocarbon residue
  • A is an ethylene group
  • x is a number from 2 to 100.
  • R4 is an aliphatic C6 to Ci8 hydrocarbon residue
  • A is an ethylene group
  • x is a number from 2 to 100.
  • R4 is derived from fatty amines ranging from C6 to Ci8 hydrocarbon groups, either linear or branched, either saturated or unsaturated, single carbon chain lengths or mixed carbon distributions, with EO ranging from 2 moles to 100 moles.
  • a coconut fatty amine ethoxylate with 10 moles of EO was used; in another preferred embodiment, an oleic amine ethoxylate with 15 moles of EO was used; in yet another preferred embodiment, a tallow alkyl amine ethoxylate with 15 moles of EO was used; in yet another preferred embodiment, a tallow propylene diamine / lauryl dipropylene triamine ethoxylate with 20 moles of EO was used.
  • the suitability of a bonding surfactant is typically determined by the HLB of the given component relative to the other component in a blend. Furthermore all components from Group 4 a, b, c and d contain an ether group may contribute to the bonding mechanism of the other components.
  • the bonding surfactant is required to have an HLB that is in-between the HLB of the other components. For example if a component from Group 1 had an HLB of 5 and a component from Group 3 had an HLB of 15 and were otherwise incompatible, the bonding surfactant requires an HLB of 10 to be most effective.
  • the solvent systems comprise a simple group of components that form the make up or remainder of the formulation.
  • the solvent system comprises one or more components selected from the group consisting of water, monohydric alkyl alcohols having 1 to 8 carbon atoms, dihydric alcohols having 2 to 6 carbon atoms and Ci to C4 alkyl ethers of said alcohols. More preferably, group 5 comprises water, methanol, ethanol, monoethylene glycol, triethylene glycol, 2-butoxyethanol, 2-ethylhexanol, isopropanol, pentanol, butanol, or mixtures thereof.
  • a blend of water and methanol is used; in another preferred embodiment a blend of water, monoethylene glycol and 2-butoxyethanol is used; in yet another preferred embodiment, a blend of water, methanol and 2-butoxyethanol is used.
  • the corrosion inhibitor of the instant invention is preferably used in heavy brines that comprise a single salt, or blend of salts, selected from sodium chloride, potassium chloride, calcium chloride, calcium bromide, calcium nitrate, zinc chloride and zinc bromide.
  • the metals that are protected by the corrosion inhibitor are most commonly carbon or mild steels; the corrosion inhibitor can also however be used to protect more exotic metallurgies such as high chromium-alloyed steels.
  • An embodiment of the invention ideally reduced the corrosion rate of a stated salt solution to below 4 mpy.
  • the corrosion inhibitor comprises an imidazoline and at least two compounds selected from Group 2 and 3 described above.
  • the said two compounds are selected from 2-mercaptoethanol, ammonium thiosulfite, thioglycolic acid, phosphoric acid 2-ethylhexylester, poly(oxy-1 ,2-ethanediyl), alpha-isotridecyl-omega-hydroxy-, phosphate.
  • the preferred embodiments also contain
  • components from Group 4 and 5 selected from morpholine derivatives, nonyl phenol ethoxylate, lauryl alkoxylated, amine alkoxylated, monoethylene glycol, 2-butoxyethanol, water, and methanol.
  • the inventive composition is preferably added to the specific heavy brine for application as corrosion inhibitor in concentrations between 100 and 10,000 mg/L.
  • concentration will depend on the heavy brine type, static conditions, materials of construction of the medium being treated, quality of the water being used to make up the heavy brine and length of time protection is to be provided to the heavy brine fluid.
  • the system provides corrosion protection in order to improve the integrity of the media being treated.
  • compositions above for application in heavy brines to be deployed in drilling and production cycle particularly as a component of drilling fluids, packer fluids, work- over fluids and completion fluids.
  • the injected heavy brine may be sodium chloride, potassium chloride, calcium chloride, calcium bromide, zinc bromide, calcium nitrate and other salt brines and mixtures thereof.
  • the instantly described corrosion inhibiting composition is added to the heavy brine and injected into the application to provide corrosion protection.
  • the injection fluid may additionally contain, other ingredients known to those familiar with the art, including but not restricted to acids, dispersants, viscosifiers, lubricity agents, scale inhibitors, friction reducers, crosslinker, surfactants, scavenger pH adjuster, iron control agents, breakers; this is especially true if any produced water (or recycled water) is used to perform the treatment.
  • Employing the embodiments of the instant invention improves nullification of the heavy brine to render it benign and non-corrosive and damaging to the integrity of the metallurgy and equipment it will be used to treat, thus allowing better integrity management and control and corrosion inhibition protection.
  • Other applications of the embodiments of the instantaneous invention include treating water for downhole injection for pressure support, treatment of water for drilling and work- over use, wettability alteration and well cleanout.
  • references to % or ppm mean volume -% or volume -ppm throughout this specification.
  • the only gas used during testing was oxygen free nitrogen.
  • RCE testing was conducted open to air to simulate high O2 presence (which would be the case in the real life, field application).
  • Static autoclave testing utilized a N2 blanket that was purged into the head space four times before final pressurization but the brine was not purged of oxygen and saturation can be assumed.
  • the metallurgy of the coupons tested was C1018 carbon steel for RCE testing and coupons manufactured from P1 10 carbon steel were used in HPHT autoclave testing. Coupons were polished mechanically using 320 grit silicon-carbide (SiC) paper, 400 grit SiC paper, then 600 grit SiC paper and rinsed with water then acetone prior to testing.
  • SiC silicon-carbide
  • the rotating cylinder electrode (RCE) tests were conducted in PyrexTM glass reaction kettles that were heated to 185 ° F.
  • the testing solution was comprised of 900 mL of heavy brine.
  • the electrode rotation rate was set at 2000 RPM, which generated a wall shear stress of 7.0 Pa.
  • Linear polarization resistance (LPR) measurements were made with a Gamry electrochemical measurement system.
  • the working electrode was made of a 1018 carbon steel (CS) cylinder with a surface area of 3.16 cm 2 .
  • a Hastelloy C276 electrode was used as a pseudo- reference, and a graphite rod was used as the counter electrode.
  • the corrosion inhibitors were added based on the brine volume after the baseline corrosion rate was monitored for approximately 1 .5 hours.
  • the electrodes were cleaned in an inhibited acid bath according to ASTM G1 C.3.5, and weighed to 0.1 mg.
  • HPHT static autoclave tests were used to simulate the zero shear conditions for the purpose of evaluating system corrosivity as well as inhibitor performance.
  • the test solution consisted of 800 ml_ of heavy brine. The head space was cleared of oxygen using 100% nitrogen gas four times before final pressurization into the autoclaves. Two weight loss corrosion coupons fixed on a PTFE cage were used in each autoclave. General corrosion rates were calculated by weight loss measurement according to ASTM G170 (and associated standards referenced therein). Test conditions were constant in all examples with a temperature of
  • the inhibitors were dosed in at a variety of dose rates ranging from 100 to 300 ppm (based on each inhibitor component) and the tests were run for 7 days.
  • the surfaces of the electrodes and coupons were analyzed after each test for pitting potential by using a high powered metallurgical microscope. The reflected light microscope was capable of analyzing samples up to 1 ,000-times
  • the microscope was mounted with a camera and included brightfield, darkfield, and Differential Interface Controls (DIC) modes.
  • DIC Differential Interface Controls
  • Corrosion Component Component Component No. Rate Group 1 Group 2 Group 3 Group 4
  • Example 2 The use of phosphate ester in Example 2 led to high corrosion inhibition performance in the three component system. More specific work was performed on phosphate ester chemistries in order to fully understand and leverage this performance. Testing was performed on a great many different phosphate ester chemistries in order to identify the most important types for higher performance corrosion inhibition of heavy brines. Again work was performed on the harshest brine 4 (13.5 Ca(NO3)2/CaCl2) at 350°F are shown below in Table 4. The results display the data from three different phosphate ester chemistries, namely
  • Ester 1 which is phosphoric acid 2-ethylhexylester
  • Ester 2 which is poly(oxy-1 ,2-ethanediyl), alpha-isotridecyl-omega- hydroxy-, phosphate; Phos. Ester 3, which is 2-Ethyl hexyl mono/di phosphoric acid ester, acid.
  • Corrosion Component Phos Phos Phos Component No. Rate Group 1 Group 2 Ester 1 Ester 2 Ester 3 Group 4
  • Imidazoline this is a primary component of the corrosion inhibitor formulations (component 1 ), as described above there are many
  • Morpholine this is used as a formulation bonding compound (component 4a) and can comprise different species of morpholine and its derivatives; in these formulations specified, an alkyl (C6) morpholine was used throughout;
  • Phosphate ester this is another primary component of the corrosion inhibitor formulations (component 3) and can comprise different species of phosphate ester; in these formulations specified, poly(oxy-1 ,2-ethanediyl), alpha-isotridecyl-omega-hydroxy-, phosphate was used throughout;
  • Thioglycolic acid this is a sulfur synergist and is another preferred embodiment of the corrosion inhibitor (component 2);
  • surfactants component 4
  • component 4 a coconut fatty acid ethoxylate with 10 moles of EO was used throughout;
  • Corrosion rates were all generally around 1 .0 mpy but in some extra-ordinary cases were as low as 0.1 mpy when further adjusting the components to optimum and synergistic concentrations.
  • Yet another unique feature of the disclosed corrosion inhibitors is the speed to achieve inhibition.
  • these prior art inventions take several days to achieve equilibrium and reduce the corrosion rate to the final claimed level. It is clearly more desirable to achieve a low corrosion rate as quickly as possible, thus enabling better protection of equipment that comes into contact with heavy brine during oilfield operations.
  • Chemical B corresponds to # 7 from Table 7.
  • Chemical C corresponds to # 1 from Table 7.
  • Chemical D corresponds to # 8 from Table 7.
  • Chemical E corresponds to # 2 from Table 7.
  • NP9 was a nonyl phenol with 9 moles ethylene oxide.
  • the alcohol ethoxylate was a C10/C12 alcohol with 4 - 8 moles of ethylene oxide.
  • the alcohol is methanol.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne une composition pouvant être utilisée en tant que composition inhibant la corrosion dans des systèmes de saumure lourde, laquelle composition comprend au moins une imidazoline, au moins un composé synergique du soufre et au moins un ester de phosphate. Dans un mode de réalisation préféré, la composition comprend, en outre, un tensioactif de liaison pour la formulation et/ou au moins un système de solvant.
PCT/EP2015/079234 2014-12-11 2015-12-10 Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde WO2016092010A1 (fr)

Priority Applications (5)

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EP15807923.6A EP3230398B1 (fr) 2014-12-11 2015-12-10 Composition d'inhibiteur de liquide et son procédé de préparation et leur application comme un contrôle de la corrosion de saumure épaisse
CA2962751A CA2962751C (fr) 2014-12-11 2015-12-10 Composition inhibitrice liquide, son procede de preparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde
EA201791291A EA034845B1 (ru) 2014-12-11 2015-12-10 Жидкая ингибирующая композиция, способ ее приготовления и применение для контроля коррозии в тяжелом солевом растворе
US15/534,307 US10611951B2 (en) 2014-12-11 2015-12-10 Liquid inhibitor composition and a method for its preparation and application as a heavy brine corrosion control
DK15807923T DK3230398T3 (da) 2014-12-11 2015-12-10 Flydende hæmmer-sammensætning og fremgangsmåde til fremstilling af denne og anvendelse som en kontrol af korrosion af en tung saltopløsning

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US201414567885A 2014-12-11 2014-12-11
US14/567,885 2014-12-11
EP15000028.9 2015-01-08
EP15000028 2015-01-08

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PCT/EP2015/079234 WO2016092010A1 (fr) 2014-12-11 2015-12-10 Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde

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WO2018093244A1 (fr) * 2016-11-18 2018-05-24 Petroliam Nasional Berhad (Petronas) Inhibiteurs de corrosion et procédés d'utilisation de ces inhibiteurs de corrosion
WO2020226996A1 (fr) * 2019-05-03 2020-11-12 Shell Oil Company Formulation d'inhibiteur de corrosion

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US10876212B2 (en) 2017-11-01 2020-12-29 Championx Usa Inc. Corrosion inhibitor compositions and methods of using same
EP3704208B1 (fr) * 2017-11-01 2021-09-01 Ecolab USA Inc. Compositions inhibitrices de la corrosion et leurs procédés d'utilisation

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US4536302A (en) 1983-06-30 1985-08-20 Nl Industries Inc Corrosion inhibition of aqueous brines
EP0139260A1 (fr) 1983-10-03 1985-05-02 The Dow Chemical Company Inhibiteurs de corrosion à base de sels de phosphonium pour saumures concentrées
EP0153192A2 (fr) 1984-02-21 1985-08-28 M-I DRILLING FLUIDS COMPANY (a Texas general partnership) Inhibiteur de corrosion pour saumures denses
US4728446A (en) 1984-07-31 1988-03-01 The Dow Chemical Company Corrosion inhibitor for brines
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US4784778A (en) 1986-09-30 1988-11-15 Great Lakes Chemical Corp. Corrosion inhibiting composition for zinc halide-based clear, high density fluids
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US4849171A (en) 1987-02-09 1989-07-18 Bruce Murray Corrosion inhibition of sodium and calcium chloride
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WO2012063055A1 (fr) 2010-11-09 2012-05-18 Champion Technologies Ltd Procédé et composition empêchant la corrosion de surfaces métalliques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018093244A1 (fr) * 2016-11-18 2018-05-24 Petroliam Nasional Berhad (Petronas) Inhibiteurs de corrosion et procédés d'utilisation de ces inhibiteurs de corrosion
WO2020226996A1 (fr) * 2019-05-03 2020-11-12 Shell Oil Company Formulation d'inhibiteur de corrosion

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CA2962751C (fr) 2022-06-07
DK3230399T3 (en) 2019-04-15
CA2962751A1 (fr) 2016-06-16
DK3230398T3 (da) 2019-10-28
EP3230398A1 (fr) 2017-10-18
EP3230399A1 (fr) 2017-10-18
EP3230398B1 (fr) 2019-08-14
WO2016092011A1 (fr) 2016-06-16
EP3230399B1 (fr) 2019-02-20
EA201791290A1 (ru) 2017-09-29
EA035934B1 (ru) 2020-09-03
CA2962753C (fr) 2022-06-07
EA034845B1 (ru) 2020-03-27
EA201791291A1 (ru) 2017-09-29
CA2962753A1 (fr) 2016-06-16

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